Unbalanced 2D Chiral Crystallization of Pentahelicene Propellers and Their Planarization into Nanographenes

The chiral self‐assembly of trispentahelicene propellers on a gold surface has been investigated in ultrahigh vacuum by means of scanning tunneling microscopy and time‐of‐flight secondary ion mass spectrometry. The trispentahelicene propellers aggregate into mirror domains with an enantiomeric ratio of 2 : 1. Thermally induced cyclodehydrogenation leads to planarization into nanographenes, which self‐assemble into closed‐packed layers with two different azimuths. Further treatment induces in part dimerization and trimerization by intermolecular cyclodehydrogenation.
From helical to planar: Molecular propellers built up by three pentahelicene subunits self‐assemble on a gold surface into enantiomerically unbalanced two‐dimensional crystal domains. Upon thermal treatment of the close‐packed monolayer, intramolecular cyclodehydrogenation into planar nanographenes occurs. Further thermal treatment leads in part to fusion into larger graphene flakes of up to four nanographene units by intermolecular cyclodehydrogenation.